Polypropylene-Based Composite

ABSTRACT

The present invention relates to a polypropylene-based composite, including (A) polypropylene, and (B) an olefin-based polymer satisfying the following conditions: (1) a melt index (MI, 190° C., 2.16 kg load conditions) is from 0.1 g/10 min to 10.0 g/10 min, (2) a melting temperature when measured by differential scanning calorimetry (DSC) is from 20° C. to 70° C., and (3) a high temperature melting peak is confirmed at 75° C. to 150° C. when measured by a differential scanning calorimetry precise measurement method (SSA), and a total enthalpy of fusion ΔH(75) of a corresponding region is 1.0 J/g or more. The polypropylene-based composite of the present invention may show excellent impact strength.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a national stage entry under 35 U.S.C. § 371of International Application No. PCT/KR2020/013278 filed on Sep. 28,2020, which claims priority from Korean Patent Application No.10-2019-0121151 filed on Sep. 30, 2019, all the disclosures of which areincorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a polypropylene-based composite, andmore particularly, to a polypropylene-based composite having improvedimpact strength and mechanical properties by including a low-densityolefin-based polymer introducing a highly crystalline region and showinghigh mechanical rigidity.

BACKGROUND ART

Generally, as a composition for car interior and exterior materialparts, a polypropylene resin composition including polypropylene (PP) asa main component, an impact reinforcing agent and an inorganic fillerhas been used.

Until the mid-1990s before developing ethylene-α-olefin copolymerspolymerized by applying a metallocene catalyst, as car interior andexterior materials, particularly, as materials for a bumper cover,ethylene propylene rubber (EPR) or ethylene propylene diene rubber(EDPM) has been mainly used in most polypropylene-based resincompositions. However, after the appearance of ethylene-α-olefincopolymers synthesized by a metallocene catalyst, the ethylene-α-olefincopolymers have been used as impact reinforcing agents, and at present,become the mainstream. Because polypropylene-based composites usingthereof have advantages in having well-balanced physical propertiesincluding impact strength, flexural modulus, flexural strength, etc.,having good moldability and being cheap in price.

Since the molecular structure of polyolefin such as ethylene-α-olefincopolymers synthesized by a metallocene catalyst is more uniformlycontrolled than that by a Ziegler-Natta catalyst, molecular weightdistribution is narrow, and mechanical properties are good overall. Fora low-density ethylene elastomer polymerized by the metallocenecatalyst, an α-olefin copolymerization monomer is relatively uniformlyinserted in a polyethylene molecule when compared with that by aZiegler-Natta catalyst, and rubber properties of a low density may bemaintained while showing excellent other mechanical properties.

However, there are limitations in securing impact resistance accordingto diverse utilizing environments, and the development of apolypropylene-based composite which may overcome such limitations isrequired.

DISCLOSURE OF THE INVENTION Technical Problem

The task to be solved of the present invention is to provide apolypropylene-based composite which may show markedly improved impactstrength properties together with excellent mechanical strength.

Technical Solution

To solve the above tasks, the present invention provides apolypropylene-based composite including (A) polypropylene, and (B) anolefin-based polymer satisfying conditions (1) to (3) below.

(1) A melt index (MI, 190° C., 2.16 kg load conditions) is from 0.1 g/10min to 10.0 g/10 min, (2) a melting temperature when measured bydifferential scanning calorimetry (DSC) is from 20° C. to 70° C., and(3) a high temperature melting peak is confirmed at 75° C. to 150° C.when measured by a differential scanning calorimetry precise measurementmethod (SSA), and a total enthalpy of fusion ΔH (75) of a correspondingregion is 1.0 J/g or more.

Advantageous Effects

The polypropylene-based composite according to the present invention mayshow markedly improved impact strength properties together withexcellent mechanical strength without using a separate additive byincluding an olefin-based polymer which introduces a highly crystallineregion and shows high mechanical rigidity and at the same time, hasexcellent miscibility and may be uniformly dispersed in the composite.

BRIEF DESCRIPTION ON DRAWINGS

FIG. 1 is a graph showing measured results of a melting temperatureusing differential scanning calorimetry (DSC) on a polymer ofPreparation Example 1.

FIG. 2 is a graph showing measured results of a melting temperatureusing differential scanning calorimetry (DSC) on a polymer ofComparative Preparation Example 1.

FIG. 3 is a graph showing measured results of a total enthalpy of fusionΔH (75) at 75° C. to 150° C. by a differential scanning calorimetryprecise measurement method (SSA) on a polymer of Preparation Example 1.

FIG. 4 is a graph showing measured results of a total enthalpy of fusionΔH (75) at 75° C. to 150° C. by a differential scanning calorimetryprecise measurement method (SSA) on a polymer of Comparative PreparationExample 1.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail toassist the understanding of the present invention.

It will be understood that words or terms used in the present disclosureand claims shall not be interpreted as the meaning defined in commonlyused dictionaries. It will be further understood that the words or termsshould be interpreted as having a meaning that is consistent with theirmeaning in the context of the relevant art and the technical idea of theinvention, based on the principle that an inventor may properly definethe meaning of the words or terms to best explain the invention.

The term “polymer” used in the present disclosure means a polymercompound prepared by polymerizing monomers which are the same ordifferent types. The common term “polymer” includes a term“interpolymer” as well as “homopolymer”, “copolymer” and “terpolymer”.In addition, the term “interpolymer” means a polymer prepared bypolymerizing two or more different types of monomers. The common term“interpolymer” includes a term “copolymer” (commonly used to refer apolymer prepared from two different monomers) and a term “terpolymer”(commonly used to refer a polymer prepared from three differentmonomers). The term “interpolymer” includes a polymer prepared bypolymerizing four or more types of monomers.

Generally, polypropylene is used as car interior and exterior materialssuch as a car bumper, and to supplement the low impact strength ofpolypropylene, a polyolefin-based polymer is used together as an impactreinforcing material. Above all, in order to show properties of impactresistance, elastic modulus and tensile properties and to achieve highimpact strength properties according to various utilizing environments,a low-density polyolefin-based polymer is used. However, in this case,there are problems of rather deteriorating the strength ofpolypropylene.

In this regard, in the present invention, by using an olefin-basedpolymer which has excellent improving effects of impact strength and atthe same time, which may be uniformly dispersed in a composite due toexcellent miscibility with polypropylene when preparing apolypropylene-based composite, markedly improved impact strengthproperties together with excellent mechanical strength may be shownwithout using a separate additive.

The polypropylene-based composite according to the present inventionincludes (A) polypropylene, and (B) an olefin-based polymer satisfyingconditions (1) to (3) below.

(1) A melt index (MI, 190° C., 2.16 kg load conditions) is from 0.1 g/10min to 10.0 g/10 min, (2) a melting temperature when measured bydifferential scanning calorimetry (DSC) is from 20° C. to 70° C., and(3) a high temperature melting peak is confirmed at 75° C. to 150° C.when measured by a differential scanning calorimetry precise measurementmethod (SSA), and a total enthalpy of fusion ΔH (75) of a correspondingregion is 1.0 J/g or more.

Hereinafter, each constituent component will be explained in detail.

(A) Polypropylene

In the polypropylene-based composite according to an embodiment of thepresent invention, the polypropylene may particularly be a homopolymerof polypropylene, or a copolymer of propylene and an alpha-olefinmonomer, and in this case, the copolymer may be an alternating orrandom, or block copolymer. However, in the present invention, thepolypropylene which may be overlapped with the olefin polymer isexcluded, and the polypropylene is a different compound from the olefinpolymer.

The alpha-olefin-based monomer may particularly be an aliphatic olefinof 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More particularly,ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eitocene,4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene,etc., may be used, and any one among them or mixtures of two or morethereof may be used.

More particularly, the polypropylene may be any one selected from thegroup consisting of a polypropylene copolymer, a propylene-alpha-olefincopolymer, and a propylene-ethylene-alpha-olefin copolymer, or mixturesof two or more thereof, and in this case, the copolymer may be a randomor block copolymer.

In addition, the melt index (MI) measured at 230° C. and a load of 2.16kg of the polypropylene may be 0.5 g/10 min to 100 g/10 min, andparticularly, the melt index (MI) may be 1 g/10 min to 90 g/10 min, moreparticularly, 10 g/10 min to 50 g/10 min. If the melt index of thepolypropylene is deviated from the range, it is apprehended that defectsmay be generated during injection molding.

Particularly, in the polypropylene-based composite according to anembodiment of the present invention, the polypropylene may be an impactcopolymer having a melt index measured at 230° C. and a load of 2.16 kgof 0.5 g/10 min to 100 g/10 min, particularly, 1 g/10 min to 90 g/10min, more particularly, may be a propylene-ethylene impact copolymer.The impact copolymer may be included in 50 wt % to 90 wt %, moreparticularly, 80 wt % to 90 wt % with respect to the total weight of thepolypropylene-based composite. In case of including the impact copolymerhaving such physical properties as polypropylene in the above-describedamount range, particularly strength properties low-temperature strengthproperties may be improved.

The impact copolymer may be prepared by using a general preparationreaction of a polymer so as to satisfy the above-described physicalproperty conditions, or may be obtained commercially and used.Particular examples may include SEETE™ M1600 of LG Chem, Co., etc.

In addition, in the polypropylene-based composite according to anembodiment of the present invention, the polypropylene may particularlybe one or more random propylene copolymers having a DSC meltingtemperature in a range of 120° C. to 160° C., and a melting flow rate(MFR) measured at 230° C. and a load of 2.16 kg according to ASTM-D 1238in a range of 5 g/10 min to 120 g/10 min, and the random propylenecopolymer may be included in 75 wt % to 97 wt %, more particularly, 85wt % to 91 wt % with respect to the total weight of thepolypropylene-based composite. If the polypropylene having such physicalproperties is included in the above-described amount range, themechanical strength of the polypropylene composite including hardness,etc. may be improved. The random propylene copolymer may be prepared soas to satisfy the above-described physical property conditions by usingthe common preparation reaction of a polymer, or may be obtainedcommercially and used. Particular examples may include Braskem™ PPR7021-50RNA of Braskem America Inc., Formolene™ 7320A of FormosaPlastics Corporation in America, etc.

(B) Olefin-Based Polymer

The olefin-based polymer included in the polypropylene-based compositeaccording to the present invention has a very low density and introducesa highly crystalline region when compared with a common conventionalolefin-based polymer, and in case of having the same degrees of densityand melt index (MI, 190° C., 2.16 kg load conditions), even highertensile strength and tearing strength may be shown. The olefin-basedpolymer included in the polypropylene-based composite according to thepresent invention is prepared by a preparation method including a stepof polymerizing an olefin-based monomer by injecting a hydrogen gas inthe presence of a catalyst composition for polymerizing olefin, andaccording to the injection of the hydrogen gas during polymerization, ahighly crystalline region is introduced, and excellent mechanicalrigidity is shown.

The melt index (MI) may be controlled by controlling an amount of thecomonomer used and that of a catalyst used in the process ofpolymerizing an olefin-based polymer and influences the mechanicalproperties and impact strength of the olefin-based polymer, and itsmoldability. In the present disclosure, the melt index is measured underlow-density conditions of 0.850 g/cc to 0.890 g/cc according to ASTMD1238 at 190° C. and 2.16 kg load conditions, and may show 0.1 g/10 minto 10 g/10 min, particularly, 0.3 g/10 min to 9 g/10 min, moreparticularly, 0.4 g/10 min to 7 g/10 min.

The melting temperature (Tm) when measured by differential scanningcalorimetry (DSC) is 20° C. to 70° C., and may particularly be 20° C. to60° C., more particularly, 25° C. to 50° C.

A high temperature melting peak is confirmed at 75° C. to 150° C. whenmeasured by a differential scanning calorimetry precise measurementmethod (SSA), and particularly, the corresponding region may be 75° C.to 145° C., more particularly, 75° C. to 135° C. In this case, the totalenthalpy of fusion ΔH (75) of the corresponding region is 1.0 J/g ormore, and may particularly be 1.0 J/g to 3.0 J/g, more particularly, 1.0J/g to 2.0 J/g.

Generally, the measurement of a melting temperature (Tm) usingdifferential scanning calorimetry is performed by a first cycleincluding heating to a temperature higher by about 30° C. than themelting temperature (Tm) at a constant rate, and cooling to atemperature lower by about 30° C. than a glass transition temperature(Tg) at a constant rate and a second cycle to obtain the peak of astandard melting temperature (Tm). The differential scanning calorimetryprecise measurement method (SSA) is a method of obtaining more accuratecrystal information by undergoing a process of heating immediatelybefore the peak of a melting temperature (Tm) and cooling after thefirst cycle using differential scanning calorimetry (DSC), andrepeatedly performing heating to a temperature reduced by about 5° C.and cooling (Eur. Polym. J. 2015, 65, 132).

In case of introducing a small amount of a highly crystalline region toan olefin-based polymer, a high temperature melting peak may not beshown when measured by a melting temperature using general differentialscanning calorimetry (DSC) but may be measured through the differentialscanning calorimetry precise measurement method (SSA).

In the olefin-based polymer, a high temperature melting peak isconfirmed in the temperature range when measured by a differentialscanning calorimetry precise measurement method (SSA), and by satisfyingthe range of the total enthalpy of fusion ΔH (75) of the correspondingregion, even higher mechanical rigidity may be attained with equivalentdegrees of density and melting index value when compared with a commonconventional olefin-based polymer.

Meanwhile, the olefin-based polymer may additionally satisfy (4) adensity of 0.850 g/cc to 0.890 g/cc, and particularly, the density maybe 0.850 g/cc to 0.880 g/cc, more particularly, 0.860 g/cc to 0.875g/cc.

Generally, the density of an olefin-based polymer is influenced by thetype and amount of a monomer used for polymerization, a polymerizationdegree, etc., and in case of a copolymer, the influence by the amount ofa comonomer is significant. The olefin-based polymer included in thepolypropylene-based composite of the present invention is polymerizedusing a catalyst composition including a transition metal compoundhaving a characteristic structure, and a large amount of comonomer maybe introduced. Accordingly, the olefin-based polymer may have a lowdensity as in the above-described range.

In addition, the olefin-based polymer may additionally satisfy theconditions of (5) a weight average molecular weight (Mw) of 10,000 g/molto 500,000 g/mol, and particularly, the weight average molecular weight(Mw) may be 30,000 g/mol to 300,000 g/mol, more particularly, 50,000g/mol to 200,000 g/mol. In the present invention, the weight averagemolecular weight (Mw) is a polystyrene conversion molecular weightanalyzed by gel permeation chromatography (GPC).

In addition, the olefin-based polymer may additionally satisfy theconditions of (6) molecular weight distribution (MWD) which is the ratio(Mw/Mn) of a weight average molecular weight (Mw) and a number averagemolecular weight (Mn), of 0.1 to 6.0, and the molecular weightdistribution (MWD) may particularly be 1.0 to 4.0, more particularly,2.0 to 3.0.

The olefin-based polymer may be any homopolymer selected from anolefin-based monomer, particularly, an alpha-olefin-based monomer, acyclic olefin-based monomer, a diene olefin-based monomer, a trieneolefin-based monomer and a styrene-based monomer, or a copolymer of twoor more. More particularly, the olefin-based polymer may be a copolymerof ethylene with alpha-olefin of 3 to 12 carbon atoms, or a copolymerwith alpha-olefin of 3 to 10 carbon atoms.

The alpha-olefin comonomer may include any one selected from the groupconsisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbonadiene,ethylidene norbornene, phenyl norbornene, vinyl norbornene,dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene,styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene,or mixtures of two or more thereof.

More particularly, the olefin-based polymer may be a copolymer ofethylene with propylene, ethylene with 1-butene, ethylene with 1-hexene,ethylene with 4-methyl-1-pentene or ethylene with 1-octene, and moreparticularly, the olefin copolymer may be a copolymer of ethylene with1-butene.

If the olefin-based polymer is the copolymer of ethylene andalpha-olefin, the amount of the alpha-olefin may be 90 wt % or less,more particularly, 70 wt % or less, further more particularly, 5 wt % to60 wt %, further more particularly, 20 wt % to 50 wt % based on thetotal weight of the copolymer. If the alpha-olefin is included in therange, the achievement of the above-described physical properties may beeasy.

The olefin-based polymer included in the polypropylene-based compositeaccording to an embodiment of the present invention having theabove-described physical properties and configurational characteristicsmay be prepared through continuous solution polymerization reaction forpolymerizing an olefin-based monomer by injecting a hydrogen gas in thepresence of a metallocene catalyst composition including one or moretypes of transition metal compounds in a single reactor. Accordingly, inthe olefin-based polymer included in the polypropylene-based compositeaccording to an embodiment of the present invention, a block composed bylinearly connecting two or more repeating units derived from any onemonomer among monomers constituting a polymer is not formed in thepolymer. That is, the olefin-based polymer included in thepolypropylene-based composite according to the present invention may notinclude a block copolymer, but may be selected from the group consistingof a random copolymer, an alternating copolymer and a graft copolymer,more particularly, a random copolymer.

In an embodiment of the present invention, the injection amount of thehydrogen gas may be 0.35 to 3 parts by weight, particularly, 0.4 to 2parts by weight, more particularly, 0.45 to 1.5 parts by weight based on1 part by weight of an olefin-based monomer injected into a reactionsystem. In addition, in an embodiment of the present invention, if theolefin-based polymer is polymerized by continuous solutionpolymerization, the hydrogen gas may be injected in an amount of 0.35 to3 kg/h, particularly, 0.4 to 2 kg/h, more particularly, 0.45 to 1.5 kg/hbased on 1 kg/h of the olefin-based monomer injected into a reactionsystem.

In addition, in another embodiment of the present invention, in casewhere the olefin-based polymer is a copolymer of ethylene andalpha-olefin, the hydrogen gas may be injected in an amount of 0.8 to 3parts by weight, particularly, 0.9 to 2.8 parts by weight, moreparticularly, 1 to 2.7 parts by weight based on 1 part by weight ofethylene. In addition, in an embodiment of the present invention, incase where the olefin-based polymer is a copolymer of ethylene andalpha-olefin and is polymerized by continuous solution polymerization,the hydrogen gas may be injected into a reaction system in an amount of0.8 to 3 kg/h, particularly, 0.9 to 2.8 kg/h, more particularly, 1 to2.7 kg/h based on 1 kg/h of ethylene.

If polymerization is performed under conditions of injecting theabove-described amount range of the hydrogen gas, the olefin-basedpolymer of the present invention may satisfy the above-describedphysical properties.

Particularly, the olefin-based copolymer included in thepolypropylene-based composite of the present invention may be obtainedby a preparation method including a step of polymerizing an olefin-basedmonomer by injecting a hydrogen gas in the presence of a catalystcomposition for polymerizing olefin, including a transition metalcompound of Formula 1 below.

However, in the preparation of the olefin-based polymer according to anembodiment of the present invention, it should be understood that therange of the structure of the transition metal compound of Formula 1 isnot limited to a specific disclosed type, but all changes, equivalentsor substituents included in the spirit and technical range of thepresent invention are included.

In Formula 1,

R₁ groups are the same or different and each independently hydrogen,alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl,silyl, alkylaryl, arylalkyl, or metalloid radical of a metal in group 4,which is substituted with hydrocarbyl, and two R₁ groups may beconnected with each other by alkylidene radical containing alkyl of 1 to20 carbon atoms or aryl radical of 6 to 20 carbon atoms to form a ring;

R₂ groups are the same or different and each independently hydrogen;halogen; alkyl of 1 to 20 carbon atoms; aryl; alkoxy; aryl oxy; or amidoradical, and two R₂ groups may be connected with each other to form analiphatic ring or an aromatic ring;

R₃ groups are the same or different and each independently hydrogen;halogen; alkyl of 1 to 20 carbon atoms; or a nitrogen-containingaliphatic or aromatic ring, which is unsubstituted or substituted witharyl radical, in case where multiple substituents are present, two ormore substituents among the substituents may be connected with eachother to form an aliphatic or aromatic ring;

M is a transition metal in group 4; and

Q₁ and Q₂ are each independently halogen; alkyl of 1 to 20 carbon atoms;alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido of 1 to 20 carbonatoms; aryl amido; or alkylidene radical of 1 to 20 carbon atoms.

In addition, in another embodiment of the present invention, in Formula1, R₁ and R₂ may be the same or different and each independentlyhydrogen; alkyl of 1 to 20 carbon atoms; aryl; or silyl,

R₃ groups may be the same or different and may be alkyl of 1 to 20carbon atoms; alkenyl of 2 to 20 carbon atoms; aryl; alkylaryl;arylalkyl; alkoxy of 1 to 20 carbon atoms; aryloxy; or amido, and two ormore R₃ groups may be connected with each other to form an aliphatic oraromatic ring;

Q₁ and Q₂ may be the same or different and each independently halogen;alkyl of 1 to 20 carbon atoms; alkyl amido of 1 to 20 carbon atoms; oraryl amido, and

M may be a transition metal in group 4.

The transition metal compound represented by Formula 1 hascharacteristics in which a metal site is connected by a cyclopentadienyl(Cp) ligand introducing tetrahydroquinoline, and a narrow Cp-M-N angleand a wide Q₁-M-Q₂ (Q₃-M-Q₄) angle to which a monomer goes near, aremaintained. In addition, according to the bonding of a ring type, Cp,tetrahydroquinoline, nitrogen and a metal site are connected in order,and more stable and rigid five-member ring structure is formed.Accordingly, in case of activating such compounds by reacting with aco-catalyst such as methylaluminoxane and B(C₆F₅)₃ and then, applyingthereof to olefin polymerization, the polymerization of an olefin-basedpolymer having the characteristics of high activity, high molecularweight and high copolymerization properties may be achieved even at ahigh polymerization temperature.

Each substituent defined in the present disclosure will be explained indetail as follows.

The term “hydrocarbyl group” used in the present disclosure means amonovalent hydrocarbon group of 1 to 20 carbon atoms, which is composedof only carbon and hydrogen irrespective of its structure, such asalkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl and arylalkyl,unless otherwise referred to.

The term “halogen” used in the present disclosure means fluorine,chlorine, bromine or iodine, unless otherwise referred to.

The term “alkyl” used in the present disclosure means a hydrocarbonresidual group of a linear chain or branched chain, unless otherwisereferred to.

The term “cycloalkyl” used in the present disclosure represents cyclicalkyl including cyclopropyl, etc., unless otherwise referred to.

The term “alkenyl” used in the present disclosure means an alkenyl groupof a linear chain or branched chain, unless otherwise referred to.

The branched chain may be alkyl of 1 to 20 carbon atoms; alkenyl of 2 to20 carbon atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20carbon atoms; or arylalkyl of 7 to 20 carbon atoms.

The term “aryl” used in the present invention represents, unlessotherwise referred to, an aromatic group of 6 to 20 carbon atoms,particularly, phenyl, naphthyl, anthryl, phenanthryl, chrysenyl,pyrenyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, etc., withoutlimitation.

The alkylaryl group means an aryl group substituted with the alkylgroup.

The arylalkyl group means an alkyl group substituted with the arylgroup.

The cyclic group (or heterocyclic group) means a monovalent aliphatic oraromatic hydrocarbon group having 5 to 20 ring-forming carbon atoms andincluding one or more heteroatoms, and may be a single ring or acondensed ring of two or more rings. In addition, the heterocyclic groupmay be unsubstituted or substituted with an alkyl group. Examplesthereof may include indoline, tetrahydroquinoline, etc., but the presentinvention is not limited thereto.

The alkyl amino group means an amino group substituted with the alkylgroup, and includes a dimethylamino group, a diethylamino group, etc.,without limitation.

According to an embodiment of the present invention, the aryl group maypreferably have 6 to 20 carbon atoms, and may particularly be phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, etc.,without limitation.

In the present disclosure, the silyl may be silyl unsubstituted orsubstituted with alkyl of 1 to 20 carbo atoms, for example, silyl,trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl,trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl,triphenylsilyl, tris(trimethylsilyl)silyl, etc., without limitation.

The compound of Formula 1 may be Formula 1-1 below, without limitation.

Besides, the compound may have various structures within the rangedefined in Formula 1.

The transition metal compound of Formula 1 may introduce a large amountof alpha-olefin as well as low-density polyethylene due to thestructural characteristics of a catalyst, and a low-density polyolefincopolymer with a degree of 0.850 g/cc to 0.890 g/cc may be prepared.

The transition metal compound of Formula 1 may be prepared by, forexample, a method below.

In Reaction 1, R₁ to R₃, M, Q₁ and Q₂ are the same as defined in Formula1.

Formula 1 may be prepared by a method disclosed in Patent Laid-open No.2007-0003071, and all contents of the patent document are included inthe present disclosure.

The transition metal compound of Formula 1 may be used as a catalyst ofpolymerization reaction as a composition type additionally including oneor more among the co-catalyst compounds represented by Formula 2,Formula 3, and Formula 4 below.

—[Al(R₄)—O]_(a)—  [Formula 2]

A(R₄)₃   [Formula 3]

[L-H]⁺[W(D)₄]⁻ or [L]⁺[W(D)₄]^(−[Formula) 4]

In Formulae 2 to 3,

R₄ groups may be the same or different from each other and eachindependently selected from the group consisting of halogen, hydrocarbylof 1 to 20 carbon atoms, and halogen-substituted hydrocarbyl of 1 to 20carbon atoms,

A is aluminum or boron,

D groups are each independently aryl of 6 to 20 carbon atoms or alkyl of1 to 20 carbon atoms, of which one or more hydrogen atoms may besubstituted with substituents, wherein the substituent is at least anyone selected from the group consisting of halogen, hydrocarbyl of 1 to20 carbon atoms, alkoxy of 1 to 20 carbon atoms and aryloxy of 6 to 20carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis acid,

W is an element in group 13, and

a is an integer of 2 or more.

Examples of the compound represented by Formula 2 may includealkylaluminoxane such as methylaluminoxane (MAO), ethylaluminoxane,isobutylaluminoxane and butylalminoxane, and a modified alkylaluminoxaneobtained by mixing two or more types of the alkylaluminoxane,particularly, methylaluminoxane, modified methylaluminoxane (MAO).

Examples of the compound represented by Formula 3 may includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tripropylaluminum, tributylaluminum,dimethylchloroaluminum,triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum,tripentylaluminum, triisopentylaluminum, trihexylaluminum,trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum,triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide,dimethylaluminumethoxide, trimethylboron, triethylboron,triisobutylboron, tripropylboron, tributylboron, etc. and particularly,may be selected from trimethylaluminum, triethylaluminum andtriisobutylaluminum.

Examples of the compound represented by Formula 4 may includetriethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron,trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron,trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,trimethylammoniumtetra(p-trifluoromethylphenyl)boron,tributylammoniumtetrapentafluorophenylboron,N,N-diethylaniliumtetraphenylboron,N,N-diethylaniliumtetrapentafluorophenylboron,diethylammoniumtetrapentafluorophenylboron,triphenylphosphoniumtetraphenylboron,trimethylphosphoniumtetraphenylboron, dimethylaniliumtetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum,tributylammoniumtetraphenylaluminum,trimethylammoniumtetraphenylaluminum,tripropylammoniumtetraphenylaluminum,trimethylammoniumtetra(p-tolyl)aluminum,tripropylammoniumtetra(p-tolyl)aluminum,triethylammoniumtetra(o,p-dimethylphenyl)aluminum,tributylammoniumtetra(p-trifluoromethylphenyl)aluminum,trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum,tributylammoniumtetrapentafluorophenylaluminum,N,N-diethylaniliniumtetraphenylaluminum,N,N-diethylaniliumtetrapentafluorophenylaluminum,diethylammoniumtetrapentatetraphenylaluminum,triphenylphosphoniumtetraphenylaluminum,trimethylphosphoniumtetraphenylaluminum,tripropylammoniumtetra(p-tolyl)boron,triethylammoniumtetra(o,p-dimethylphenyl)boron,triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, ortriphenylcarboniumtetrapentafluorophenylboron.

The catalyst composition may be prepared by, as a first method, apreparation method including a step of obtaining a mixture by contactingthe transition metal compound represented by Formula 1 with the compoundrepresented by Formula 2 or Formula 3; and a step of adding the compoundrepresented by Formula 4 to the mixture.

In addition, the catalyst composition may be prepared by, as a secondmethod, a method of making contacting of the transition metal compoundrepresented by Formula 1 with the compound represented by Formula 4.

In the first method in the preparation method of the catalystcomposition, the molar ratio of the transition metal compoundrepresented by Formula 1 and the transition metal compound representedby Formula 2/the compound represented by Formula 2 or Formula 3 may be1/5,000 to 1/2, particularly, 1/1,000 to 1/10, more particularly, 1/500to 1/20. If the molar ratio of the transition metal compound representedby Formula 1/the compound represented by Formula 2 or Formula 3 isgreater than 1/2, the amount of an alkylating agent is too small, andthe alkylation of a metal compound may be incompletely carried out, andif the molar ratio is less than 1/5,000, the alkylation of the metalcompound may be achieved, but the activation of the alkylated metalcompound may be incompletely carried out due to the side reactionsbetween an excessive amount of the alkylating agent remained and anactivating agent which is the compound of Formula 4. In addition, themolar ratio of the transition metal compound represented by Formula1/the compound represented by Formula may be 1/25 to 1, particularly,1/10 to 1, more particularly, 1/5 to 1. If the molar ratio of thetransition metal compound represented by Formula 1/the compoundrepresented by Formula 4 is greater than 1, the amount of an activatingagent is relatively small, and the activation of the metal compound maybe incompletely carried out, and thus, the activity of the catalystcomposition may be deteriorated. If the molar ratio is less than 1/25,the activation of the metal compound may be completely carried out, butdue to the excessive amount of the activating agent remained, it wouldnot be economical considering the unit cost of the catalyst composition,or the purity of a polymer produced may be degraded.

In the second method in the preparation method of the catalystcomposition, the molar ratio of the transition metal compoundrepresented by Formula 1/the compound represented by Formula 4 may be1/10,000 to 1/10, particularly, 1/5,000 to 1/100, more particularly,1/3,000 to 1/500. If the molar ratio is greater than 1/10, the amount ofan activating agent is relatively small, and the activation of the metalcompound may be incompletely carried out, and the activity of thecatalyst composition thus produced may be degraded. If the molar ratiois less than 1/10,000, the activation of the metal compound may becompletely carried out, but due to the excessive amount of theactivating agent remained, it would not be economical considering theunit cost of the catalyst composition, or the purity of a polymerproduced may be degraded.

As the reaction solvent during preparing the catalyst composition, ahydrocarbon-based solvent such as pentane, hexane, and heptane, or anaromatic solvent such as benzene and toluene may be used.

In addition, the catalyst composition may include the transition metalcompound and the co-catalyst compound in a supported type on a support.

Any supports used in a metallocene-based catalyst may be used as thesupport without specific limitation. Particularly, the support may besilica, silica-alumina or silica-magnesia, and any one among them ormixtures of two or more thereof may be used.

In case where the support is silica among them, since a silica supportand the functional group of the metallocene compound of Formula 1 mayform a chemical bond, there is no catalyst separated from the surfaceduring an olefin polymerization process. As a result, the generation offouling, by which polymer particles are agglomerated on the wall side ofa reactor or from each other during the preparation process of anolefin-based copolymer, may be prevented. In addition, the particleshape and apparent density of a polymer of the olefin-based copolymerprepared in the presence of a catalyst including the silica support areexcellent.

More particularly, the support may be silica or silica-alumina,including a highly reactive siloxane group and dried at a hightemperature through a method of drying at a high temperature, etc.

The support may further include an oxide, a carbonate, a sulfate, or anitrate component such as Na₂O, K₂CO₃, BaSO₄ and Mg(NO₃)₂.

The polymerization reaction for polymerizing the olefin-based monomermay be achieved by a common process applied to the polymerization of anolefin monomer such as continuous solution polymerization, bulkpolymerization, suspension polymerization, slurry polymerization andemulsion polymerization.

The polymerization reaction of the olefin monomer may be performed in aninert solvent, and as the inert solvent, benzene, toluene, xylene,cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane,n-hexane, 1-hexene, and 1-octene may be used, without limitation.

The polymerization of the olefin-based polymer may be performed at atemperature of about 25° C. to about 500° C., particularly, at atemperature of 80° C. to 250° C., more preferably, 100° C. to 200° C. Inaddition, the reaction pressure during the polymerization may be 1kgf/cm² to 150 kgf/cm², preferably, 1 kgf/cm² to 120 kgf/cm², morepreferably, 5 kgf/cm² to 100 kgf/cm².

MODE FOR CARRYING OUT THE INVENTION Examples

Hereinafter, embodiments of the present invention will be explained indetail so that a person skilled in the art where the present inventionbelongs could easily perform. However, the present invention may beaccomplished in various different types and is not limited to theembodiments explained herein.

Catalyst Preparation Example 1: Preparation of Transition Metal CompoundA

(1) Preparation of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline(i) Preparation of lithium carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150mL) were put in a shlenk flask. Into a low-temperature bath of −78° C.obtained by dry ice and acetone, the shlenk flask was immersed andstirred for 30 minutes. Then, n-BuLi (39.9 mL, 2.5 M, 98.24 mmol) wasinjected under a nitrogen atmosphere via a syringe, and a light yellowslurry was formed. Then, the flask was stirred for 2 hours, and thetemperature of the flask was elevated to room temperature while removinga butane gas produced. The flask was immersed again into thelow-temperature bath of −78° C. to reduce the temperature, and a CO₂ gaswas injected. According to the injection of the carbon dioxide gas, theslurry disappeared into a transparent solution. The flask was connectedwith a bubbler, and the temperature was elevated to room temperaturewhile removing the carbon dioxide gas. After that, remaining CO₂ gas andsolvents were removed under vacuum. After transporting the flask to adry box, pentane was added thereto, followed by vigorous stirring andfiltering to obtain lithium carbamate as a white solid compound. In thewhite solid compound, diethyl ether made a coordination bond. In thiscase, the yield was 100%.

¹H NMR(C₆D₆, C₅D₅N): δ 1.90 (t, J=7.2 Hz, 6H, ether), 1.50 (br s, 2H,quin-CH₂), 2.34 (br s, 2H, quin-CH₂), 3.25 (q, J=7.2 Hz, 4H, ether),3.87 (br, s, 2H, quin-CH₂), 6.76 (br d, J=5.6 Hz, 1H, quin-CH) ppm

¹³H NMR(C₆D₆): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57,142.04, 163.09(C═O) ppm

(ii) Preparation of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i)above was put in a shlenk flask. Then, tetrahydrofuran (4.6 g, 63.9mmol) and 45 mL of diethyl ether were added thereto in order. Into alow-temperature bath of −20° C. obtained by acetone and a small amountof dry ice, the shlenk flask was immersed and stirred for 30 minutes,and n-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was injected. In this case, thecolor of the reaction mixture was changed into red. While continuouslymaintaining −20° C., stirring was performed for 6 hours. A CeCl₃.2LiClsolution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran andtetramethylcyclopentanone (5.89 g, 42.60 mmol) were mixed in a syringeand then injected into the flask under a nitrogen atmosphere. In themiddle of slowly elevating the temperature of the flask to roomtemperature, a thermostat was removed after 1 hour, and the temperaturewas maintained to room temperature. Then, water (15 mL) was added to theflask, and ethyl acetate was put, followed filtering to obtain afiltrate. The filtrate was transported to a separating funnel, andhydrochloric acid (2 N, 80 mL) was added thereto, followed by shakingfor 12 minutes. Then, a saturated sodium bicarbonate solution (160 mL)was added to neutralize, and an organic layer was extracted. To theorganic layer, anhydrous magnesium sulfate was put to remove moisture,and filtering was conducted. The filtrate was taken, and solvents wereremoved. The filtrate thus obtained was separated by a columnchromatography method using a solvent of hexane and ethyl acetate (v/v,10:1) to obtain a yellow oil. The yield was 40%.

¹H NMR(C₆D₆): δ 1.00 (br d, 3H, Cp-CH₃), 1.63-1.73 (m, 2H, quin-CH₂),1.80 (s, 3H, Cp-CH₃), 1.81 (s, 3H, Cp-CH₃). 1.85 (s, 3H, Cp-CH₃), 2.64(t, J=6.0 Hz, 2H, quin-CH₂). 2.84-2.90 (br, 2H, quin-CH₂), 3.06 (br s,1H, Cp-H), 3.76 (br s, 1H, N—H), 6.77 (t, J=7.2 Hz, 1H, quin-CH), 6.92(d, J=2.4 Hz, 1H, quin-CH), 6.94 (d, J=2.4 Hz, 1H, quin-CH) ppm

(2) Preparation of[(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵κ-N]titaniumdimethyl

(i) Preparation of[(1,2,3,4-tetrahydroquinoline-8-yl)tetramethylcyclopentadienyl-η⁵, κ-N]dilithium compound

In a dry box,8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline(8.07 g, 32.0 mmol) prepared through step (1) above, and 140 mL ofdiethyl ether were put in a round flask, the temperature was reduced to−30° C., and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added whilestirring. The reaction was performed for 6 hours while elevating thetemperature to room temperature. After that, washing with diethyl etherwas conducted several times, and filtering was conducted to obtain asolid. Remaining solvents were removed by applying vacuum to obtain adilithium compound (9.83 g) as a yellow solid. The yield was 95%.

¹H NMR(C₆D₆, C₅D₅N): δ 2.38 (br s, 2H, quin-CH₂), 2.53 (br s, 12H,Cp-CH₃), 3.48 (br s, 2H, quin-CH₂), 4.19 (br s, 2H, quin-CH₂), 6.77 (t,J=6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H,quin-CH) ppm

(ii) Preparation of[(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η⁵,κ-N]titanium dimethyl

In a dry box, TiCl₄.DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL)were put in a round flask, and while stirring at −30° C., MeLi (21.7 mL,31.52 mmol, 1.4 M) was slowly added. After stirring for 15 minutes, the(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-ηη⁵,κ-N]dilithium compound (5.30 g, 15.78 mmol) prepared in step (i) abovewas put in the flask. While elevating the temperature to roomtemperature, stirring was conducted for 3 hours. After finishing thereaction, vacuum was applied to remove solvents, and the resultantresidue was dissolved in pentane and filtered, and the filtrate wastaken. By removing pentane by applying vacuum, a dark brown compound(3.70 g) was obtained. The yield was 71.3%.

¹H NMR(C₆D₆): δ 0.59 (s, 6H, Ti—CH₃), 1.66 (s, 6H, Cp-CH₃), 1.69 (br t,J=6.4 Hz, 2H, quin-CH₂), 2.05 (s, 6H, Cp-CH₃), 2.47 (t, J=6.0 Hz, 2H,quin-CH₂), 4.53 (m, 2H, quin-CH₂), 6.84 (t, J=7.2 Hz, 1H, quin-CH), 6.93(d, J=7.6 Hz, quin-CH), 7.01 (d, J=6.8 Hz, quin-CH) ppm

¹³C NMR(C₆D₆): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96,120.95, 126.99, 128.73, 131.67, 136.21 ppm

Catalyst Preparation Example 2: Preparation of Transition Metal CompoundB

(1) Preparation of2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline

2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline wasprepared through the same method as in (1) in Preparation Example 1except for using 2-methylindoline instead of 1,2,3,4-tetrahydroquinolinein (1) of Preparation Example 1. The yield was 19%.

¹H NMR (C₆D₆): δ 6.97(d, J=7.2 Hz, 1H, CH), δ 6.78(d, J=8 Hz, 1H, CH), δ6.67 (t, J=7.4 Hz, 1H, CH), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s,1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH₂, Cp-CH), δ 2.65 (m, 1H,quinoline-CH²), δ 1.89 (s, 3H, Cp-CH₃), δ 1.84 (s, 3H, Cp-CH₃), δ 1.82(s, 3H, Cp-CH₃), δ 1.13 (d, J=6 Hz, 3H, quinoline-CH₃), δ 0.93 (3H,Cp-CH₃) ppm.

(2) Preparation of[(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titaniumdimethyl

(i) A dilithium salt compound (compound 4 g) coordinated with 0.58equivalent of diethyl ether was obtained (1.37 g, 50%) through the samemethod as in (2) (i) in Preparation Example 1 except for using2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g,8.88 mmol) instead of8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline.

¹H NMR(Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6 Hz, 1H, CH),δ 6.32(t, 1H, CH), δ 4.61 (brs, 1H, CH), δ 3.54 (m, 1H, CH), δ 3.00 (m,1H, CH), δ 2.35-2.12 (m, 13H, CH, Cp-CH₃), δ 1.39 (d, indoline-CH₃) ppm.

(ii) A titanium compound was prepared through the same method as in (2)(ii) in Preparation Example 1 using the dilithium salt compound(compound 4 g) (1.37 g, 4.44 mmol) prepared in (i) above.

¹H NMR (C₆D₆): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4 Hz, 1H, CH),

δ 4.96 (m, 1H, CH), δ 2.88 (m, 1H, CH), δ 2.40 (m, 1H, CH), δ 2.02 (s,3H, Cp-CH₃), δ 2.01 (s, 3H, Cp-CH₃), δ 1.70 (s, 3H, Cp-CH₃), δ 1.69 (s,3H, Cp-CH₃), δ 1.65 (d, J=6.4 Hz, 3H, indoline-CH₃), δ 0.71 (d, J=10 Hz,6H, TiMe₂—CH₃) ppm.

Preparation Example 1

To a 1.5 L continuous process reactor, a hexane solvent (5 kg/h) and1-butene (0.95 kg/h) were charged, and the temperature of the top of thereactor was pre-heated to 140.7° C. A triisobutylaluminum compound (0.06mmol/min), the transition metal compound B (0.40 μmol/min) obtained inPreparation Example 2, and a dimethylaniliniumtetrakis(pentafluorophenyl) borate co-catalyst (1.20 μmol/min) wereinjected at the same time into the reactor. Then, a hydrogen gas (15cc/min) and ethylene (0.87 kg/h) were injected into the reactor, andcopolymerization reaction was performed by maintaining 141° C. for 30minutes or more in a continuous process with a pressure of 89 bar toobtain a copolymer. After drying in a vacuum oven for 12 hours or more,physical properties were measured.

Preparation Examples 2 to 5

Copolymers were obtained by performing the same copolymerizationreaction as in Preparation Example 1 except for changing the amount usedof a transition metal compound, the amounts used of a catalyst and aco-catalyst, the reaction temperature, the injection amount of hydrogenand the amount of a comonomer as in Table 1 below.

Comparative Preparation Example 1

DF610 of Mitsui Chemicals Inc. was purchased and used.

Comparative Preparation Examples 2 to 4

Copolymers were obtained by performing the same copolymerizationreaction as in Preparation Example 1 except for changing the type of atransition metal compound, the amount used of a transition metalcompound, the amounts used of a catalyst and a co-catalyst, the reactiontemperature, the injection amount of hydrogen and the amount of acomonomer as in Table 1 below.

Comparative Preparation Example 5

DF710 of Mitsui Chemicals Inc. was purchased and used.

Comparative Preparation Example 6

DF640 of Mitsui Chemicals Inc. was purchased and used.

Comparative Preparation Example 7

EG7447 of Dow Co. was purchased and used.

TABLE 1 Catalyst amount Reaction used Co-cat. TiBAl Ethylene Hexane1-butene Hydrogen temp. Catalyst type (μmol/min) (μmol/min) (mmol/min)(kg/h) (Kg/h) (kg/h) (cc/min) (° C.) Preparation Transition 0.40 1.200.06 0.87 5 0.95 15 141 Example 1 metal compound B PreparationTransition 0.60 1.80 0.05 0.87 7 0.93 32 145 Example 2 metal compound BPreparation Transition 0.45 1.35 0.04 0.87 7 0.75 15 145 Example 3 metalcompound B Preparation Transition 0.74 2.22 0.05 0.87 7 0.93 25 150Example 4 metal compound B Preparation Transition 0.55 1.65 0.04 0.87 70.84 38 148 Example 5 metal compound B Comparative Transition 0.78 2.340.06 0.87 5 1.15 — 161 Preparation metal Example 2 compound BComparative Transition 0.32 0.96 0.05 0.87 5 0.62 — 145 Preparationmetal Example 3 compound A Comparative Transition 0.50 1.50 0.06 0.87 51.15 10 161 Preparation metal Example 4 compound B

Experimental Example 1: Evaluation of Physical Properties ofOlefin-Based Polymer

With respect to the copolymers of Preparation Examples 1 to 5, andComparative Preparation Examples 1 to 4, physical properties wereevaluated according to the methods below and are shown in Tables 2 and 3below.

1) Density of Polymer

Measurement was conducted according to ASTM D-792.

2) Melt Index (MI) of Polymer

Measurement was conducted according to ASTM D-1238 (condition E, 190°C., 2.16 kg load).

3) Weight Average Molecular Weight (Mw, g/mol) and Molecular WeightDistribution (MWD)

A number average molecular weight (Mn) and a weight average molecularweight (Mw) were measured respectively, using gel permeationchromatography (GPC), and molecular weight distribution was calculatedthrough dividing the weight average molecular weight by the numberaverage molecular weight.

-   -   Column: PL Olexis    -   Solvent: trichlorobenzene (TCB)    -   Flow rate: 1.0 ml/min    -   Specimen concentration: 1.0 mg/ml    -   Injection amount: 200 μl    -   Column temperature: 160° C.    -   Detector: Agilent High Temperature RI detector    -   Standard: Polystyrene (calibrated by cubic function)

4) Melting Temperature (Tm) of Polymer

The melting temperature was obtained using a differential scanningcalorimeter (DSC: differential scanning calorimeter 250) manufactured byTA instrument Co. That is, the temperature was elevated to 150° C., keptfor 1 minute, and reduced to −100° C., and then, the temperature waselevated again. The apex of a DSC curve was set to the melting point.

In this case, the elevating rate and reducing rate of the temperaturewere controlled to 10° C./min, and the melting temperature was obtainedduring the second elevation of the temperature.

The DSC graph of the polymer of Preparation Example 1 is shown in FIG.1, and the DSC graph of the polymer of Comparative Preparation Example 1is shown in FIG. 2.

5) High Temperature Melting Peak of Polymer and Total Enthalpy of FusionΔH (75) at 75° C. or More

Measurement was conducted by using a differential scanning calorimeter(DSC: differential scanning calorimeter 250) manufactured by TAinstrument Co. and by a successive self-nucleation/annealing (SSA)measurement method.

Particularly, in the first cycle, the temperature was elevated to 150°C., kept for 1 minute, and reduced to −100° C. In the second cycle, thetemperature was elevated to 120° C., kept for 30 minutes, and reduced to−100° C. In the third cycle, the temperature was elevated to 110° C.,kept for 30 minutes, and reduced to −100° C. As described above, aprocess of elevating the temperature and decreasing to −100° C. by aninterval of 10° C. was repeated to −60° C. so as to crystallize in eachtemperature section.

In the last cycle, the temperature was elevated to 150° C., and heatcapacity was measured. Then, the enthalpies of fusion at 75° C. or morewere combined to obtain ΔH (75).

FIG. 3 shows an SSA graph of the polymer of Preparation Example 1, andFIG. 4 shows an SSA graph of the polymer of Comparative PreparationExample 1.

6) Hardness (Shore A)

Hardness was measured according to the standard of ASTM D2240 usingGC610 STAND for durometer of TECLOCK Co. and a shore durometer Type A ofMitutoyo Co.

7) Tensile Strength and Tearing Strength of Polymer

The olefin-based copolymers of Preparation Example 1 and ComparativePreparation Examples 1 to 3 were extruded to manufacture pallet shapes,and tensile strength and tearing strength when broken were measuredaccording to ASTM D638 (50 mm/min).

TABLE 2 SSA DSC The existence of Density MI Mw Tm high temperature ΔH(75) (g/mL) (g/10 min) (g/mol) MWD (° C.) melting peak (J/g) Preparation0.862 1.20 106,000 2.01 32.1 Exist 1.04 Example 1 Preparation 0.866 4.3969,070 2.07 33.0 Exist 1.61 Example 2 Preparation 0.872 1.22 99,068 2.0545.9 Exist 1.11 Example 3 Preparation 0.866 3.30 70,000 2.11 37.8 Exist1.05 Example 4 Preparation 0.865 5.10 75,388 2.09 37.2 Exist 1.12Example 5 Comparative 0.861 1.32 105,000 1.98 39.7 None 0 PreparationExample 1 Comparative 0.861 1.12 102,000 2.11 28.6 Exist 0.71Preparation Example 2 Comparative 0.862 1.20 91,419 2.18 28.5 Exist 0.56Preparation Example 3 Comparative 0.862 1.23 100,423 2.185 29.9 Exist0.61 Preparation Example 4 Comparative 0.869 1.20 92,000 2.04 49.3 None0 Preparation Example 5 Comparative 0.865 3.40 71,000 2.04 43.8 None 0Preparation Example 6 Comparative 0.868 5.10 76,735 2.14 44.2 None 0.48Preparation Example 7

TABLE 3 SSA Density MI DSC ΔH (75) Tensile Tearing Hardness (g/mL) (g/10min) MWD Tm (° C.) (J/g) strength strength (Shore A) Preparation 0.8621.20 2.01 32.1 1.04 2.2 29.5 55.0 Example 1 Comparative 0.861 1.32 1.9839.7 0 2.1 25.6 56.7 Preparation Example 1 Comparative 0.861 1.12 2.1128.6 0.71 1.6 22.4 52.9 Preparation Example 2 Comparative 0.862 1.202.18 28.5 0.56 1.3 16.7 51.6 Preparation Example 3

When comparing the olefin-based polymer of Preparation Example 1 and theolefin-based polymer of Comparative Preparation Example 1, having theequivalent degrees of density and MI, FIG. 1 and FIG. 2 measured by DSCshowed analogical tendency and similar graph types, and no significantdifference was confirmed. However, in FIG. 3 and FIG. 4 measured by SSA,it could be confirmed that there was a significant difference in a hightemperature region of 75° C. or more. Particularly, Preparation Example1 showed peaks at 75° C. or more, but the Comparative PreparationExample did not show. Comparative Preparation Example 2 and ComparativePreparation Example 3 showed peaks in the corresponding region, but thesizes were small when compared with the Preparation Example. Due to sucha difference of the high temperature melting peaks measured by SSA,Preparation Example 1 showed a ΔH (75) value of 1.0 J/g or more, but theComparative Preparation Examples showed ΔH (75) values of less than 1.0J/g or no peaks in a corresponding region.

Through Table 3, the mechanical strength of Preparation Example 1 andComparative Preparation Examples 1, 2, and 3, having equivalent degreesof density and MI may be compared. It could be found that PreparationExample 1 introduced a polymer melted at a high temperature and showedincreased mechanical rigidity, and thus, attained increased tensilestrength and tearing strength when compared with Comparative Examples 1to 3.

Preparation Examples 1 to 5 correspond to polymers obtained bypolymerizing an olefin-based monomer by injecting a hydrogen gas andintroducing a highly crystalline region. Accordingly, high melting peakswere shown, and the ΔH (75) values of 1.0 J/g or more and highmechanical rigidity were shown. Through the comparison with ComparativePreparation Example 2 and Comparative Preparation Example 4, it could beconfirmed that the satisfaction or dissatisfaction of the ΔH (75) valueof 1.0 J/g or more and the mechanical rigidity were changed according tothe injection or not and the injection amount of a hydrogen gas duringpolymerization.

Example 1: Preparation of polypropylene-based Composite

To 20 parts by weight of the olefin copolymer prepared in PreparationExample 1, 60 parts by weight of highly crystalline impact copolymerpolypropylene (CB5230, Korea Petrochemical Industrial Co. Ltd.) having amelt index (230° C., 2.16 kg) of 30 g/10 min, and 20 parts by weight oftalc (KCNAP-400™, Coats Co.) (average particle diameter (D₅₀)=11.0 μm)were added, and then, 0.1 parts by weight of AO 1010 (Ciba SpecialtyChemicals) as an antioxidant, 0.1 parts by weight oftris(2,4-di-tert-butylphenyl)phosphite (AO 168), and 0.3 parts by weightof calcium stearate (Ca-St) were added. Then, the resultant mixture wasmelted and mulled using a twin screw extruder to prepare apolypropylene-based composite compound in a pellet shape. In this case,the twin screw extruder has a diameter of 25 Φ and a ratio of length todiameter of 40, and conditions were set to a barrel temperature of 200°C. to 230° C., a screw rotation velocity of 250 rpm, and an extrusionrate of 25 kr/hr.

Examples 2 to 5: Preparation of polypropylene-based Composites

Polypropylene-based composites were prepared by the same method as inExample 1 except for using the olefin copolymers shown in Table 4 belowinstead of the olefin copolymer prepared in Preparation Example 1. Inthis case, the type of polypropylene, and the ratio of olefin copolymerand polypropylene were changed in Example 5.

In Table 4 below, polypropylene represented by CB5290 is highlycrystalline impact copolymer polypropylene (CB5290, Korea PetrochemicalIndustrial Co. Ltd.) having a melt index (230° C., 2.16 kg) of 90 g/10min.

Comparative Examples 1 to 7: Preparation of polypropylene-basedComposites

Polypropylene-based composites were prepared by the same method as inExample 1 except for using the olefin copolymers shown in Table 4 belowinstead of the olefin copolymer prepared in Preparation Example 1. Inthis case, the type of polypropylene, and the ratio of olefin copolymerand polypropylene were changed in Comparative Example 7.

In Table 4 below, polypropylene represented by CB5290 is highlycrystalline impact copolymer polypropylene (CB5290, Korea PetrochemicalIndustrial Co. Ltd.) having a melt index (230° C., 2.16 kg) of 90 g/10min.

TABLE 4 Compounding ratio Olefin- Olefin- based based poly- polymer PPTalc polymer propylene (wt %) (wt %) (wt %) Example 1 Preparation CB523020 60 20 Example 1 Example 2 Preparation CB5230 20 60 20 Example 3Example 3 Preparation CB5230 20 60 20 Example 4 Example 4 PreparationCB5230 20 60 20 Example 5 Example 5 Preparation CB5290 30 50 20 Example3 Comparative Comparative CB5230 20 60 20 Example 1 Preparation Example1 Comparative Comparative CB5230 20 60 20 Example 2 Preparation Example2 Comparative Comparative CB5230 20 60 20 Example 3 Preparation Example3 Comparative Comparative CB5230 20 60 20 Example 4 Preparation Example5 Comparative Comparative CB5230 20 60 20 Example 5 Preparation Example6 Comparative Comparative CB5230 20 60 20 Example 6 Preparation Example7 Comparative Comparative CB5290 30 50 20 Example 7 Preparation Example5

Experimental Example 2: Evaluation of Physical Properties ofpolypropylene-based Composite

In order to confirm the physical properties of the polypropylene-basedcomposites prepared in Examples 1 to 5, and Comparative Examples 1 to 7,specimens were manufactured by injection molding the polypropylene-basedcomposites using an injection machine at a temperature of 230° C., andthe specimens were stood in a constant temperature and humidity room for1 day, and then, the specific gravity of polymers, the melt index ofpolymers, tensile strength, flexural strength and flexural modulus,impact strength at low temperature and room temperature, and contractionratio were measured. The physical properties of the specimens thusmanufactures are shown in Table 5 below.

1) Specific Gravity

Measurement was conducted according to ASTM D792.

2) Melt Index (M1) of Polymer

The melt index (MI) of a polymer was measured according to ASTM D-1238(condition E, 230° C., 2.16 kg load).

3) Tensile Strength and Flexural Strength

Measurement was conducted using INSTRON 3365 apparatus according to ASTMD790.

4) Impact Strength at Low Temperature and at Room Temperature

Measurement was conducted according to ASTM D256, impact strength atroom temperature was measured under room temperature (23° C.)conditions, and impact strength at low temperature was measured in alow-temperature chamber (−30° C.) after standing for 12 hours or more.

TABLE 5 Impact Impact strength strength Specific MI Tensile Flexural atlow at room gravity (g/10 min) strength strength temperature temperatureExample 1 1.033 14.3 211 341 4.7 42.1 Comparative 1.041 14.6 211 336 4.743.9 Example 1 Comparative 1.030 13.9 206 334 4.8 42.5 Example 2Comparative 1.038 13.9 205 327 4.7 40.9 Example 3 Example 2 1.037 14.6219 344 3.6 34.5 Comparative 1.03 15.0 216 340 3.8 37.3 Example 4Example 3 1.032 17.0 239 336 3.8 34.8 Comparative 1.032 17.4 238 334 3.834.5 Example 5 Example 4 1.036 17.7 217 336 4.3 32.9 Comparative 1.03117.8 217 333 4.4 33.1 Example 6 Example 5 1.031 16.2 171 246 8.4 53.7Comparative 1.033 16.7 168 241 9.0 52.8 Example 7

Referring to Table 5, when comparing the polypropylene-based compositesincluding olefin-based copolymers having equivalent degrees of densityand MI values, it could be confirmed that the polypropylene-basedcomposites of the Examples maintained similar degrees of impact strengthat low temperature and impact strength at room temperature, and improvedmechanical strength such as tensile strength and flexural strength whencompared with the polypropylene-based composites of the ComparativeExamples. Through this, it could be confirmed that the mechanicalrigidity of the polypropylene-based composite was improved by includingan olefin-based copolymer introducing a highly crystalline region andshowing high mechanical rigidity in the polypropylene-based composite ofthe Example.

1. A polypropylene-based composite, comprising: (A) polypropylene, and(B) an olefin-based polymer satisfying the following conditions (1) to(3): (1) a melt index (MI, 190° C., 2.16 kg load conditions) is from 0.1g/10 min to 10.0 g/10 min, (2) a melting temperature when measured bydifferential scanning calorimetry (DSC) is from 20° C. to 70° C., and(3) a high temperature melting peak is confirmed at 75° C. to 150° C.when measured by a differential scanning calorimetry precise measurementmethod (SSA), and a total enthalpy of fusion ΔH (75) of thecorresponding region of 75° C. to 150° C. is 1.0 J/g or more.
 2. Thepolypropylene-based composite according to claim 1, wherein thepolypropylene has a melt index measured at 230° C. and 2.16 kg load of0.5 g/10 min to 100 g/10 min.
 3. The polypropylene-based compositeaccording to claim 1, wherein the polypropylene is an impact copolymerhaving a melt index measured at 230° C. and 2.16 kg load of 0.5 g/10 minto 100 g/10 min.
 4. The polypropylene-based composite according to claim1, wherein the olefin-based polymer additionally satisfies the followingconditions: (4) a density (d) is 0.850 g/cc to 0.890 g/cc.
 5. Thepolypropylene-based composite according to claim 1, wherein theolefin-based polymer additionally satisfies the following conditions:(5) a weight average molecular weight (Mw) is from 10,000 g/mol to500,000 g/mol.
 6. The polypropylene-based composite according to claim1, wherein the olefin-based polymer additionally satisfies the followingconditions: (6) a molecular weight distribution (MWD) is from 0.1 to6.0.
 7. The polypropylene-based composite according to claim 1, whereinthe olefin-based polymer is a copolymer of ethylene and an alpha-olefincomonomer of 3 to 12 carbon atoms.
 8. The polypropylene-based compositeaccording to claim 7, wherein the alpha-olefin comonomer comprises anyone selected from the group consisting of propylene, 1-butene,1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene,norbornene, norbonadiene, ethylidene norbornene, phenyl norbornene,vinyl norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene,1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and3-chloromethylstyrene, or mixtures of two or more thereof.
 9. Thepolypropylene-based composite according to claim 1, wherein theolefin-based polymer is a copolymer of ethylene and 1-hexene.
 10. Thepolypropylene-based composite according to claim 1, wherein theolefin-based polymer is obtained by a preparation method comprising:polymerizing an olefin-based monomer by injecting a hydrogen gas in thepresence of a catalyst composition for polymerizing olefin, the catalystcomposition comprising a transition metal compound of the followingFormula 1:

in Formula 1, R₁ groups are the same or different and each independentlyhydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbonatoms, aryl, silyl, alkylaryl, arylalkyl, or metalloid radical of ametal in group 4, which is substituted with hydrocarbyl, and two R₁groups are optionally connected with each other by alkylidene radicalcontaining alkyl of 1 to 20 carbon atoms or aryl radical of 6 to 20carbon atoms to form a ring; R₂ groups are the same or different andeach independently hydrogen; halogen; alkyl of 1 to 20 carbon atoms;aryl; alkoxy; aryl oxy; or amido radical, and two R₂ groups areoptionally connected with each other to form an aliphatic ring or anaromatic ring; R₃ groups are the same or different and eachindependently hydrogen; halogen; alkyl of 1 to 20 carbon atoms; or anitrogen-containing aliphatic or aromatic ring, which is unsubstitutedor substituted with aryl radical, two or more R₃ groups are optionallyconnected with each other to form an aliphatic or aromatic ring; M is atransition metal in group 4; and Q₁ and Q₂ are each independentlyhalogen; alkyl of 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl;arylalkyl; alkyl amido of 1 to 20 carbon atoms; aryl amido; oralkylidene radical of 1 to 20 carbon atoms.
 11. The polypropylene-basedcomposite according to claim 1, wherein the olefin-based polymer isprepared by continuous solution polymerization reaction using acontinuous stirred tank reactor by injecting hydrogen in the presence ofa catalyst composition for polymerizing olefin.
 12. Thepolypropylene-based composite according to claim 1, wherein thepolypropylene-based composite comprises the olefin-based polymer in 5 wt% to 40 wt %.
 13. The polypropylene-based composite according to claim1, wherein the polypropylene-based composite additionally comprises aninorganic filler.
 14. The polypropylene-based composite according toclaim 13, wherein the polypropylene-based composite comprises theinorganic filler in an amount of 0.1 parts by weight to 40 parts byweight based on 100 parts by weight of the polypropylene, and theinorganic filler has an average particle diameter (D₅₀) of 1 μm to 20μm.
 15. The polypropylene-based composite according to claim 1, whereinthe polypropylene is any one selected from the group consisting of apolypropylene copolymer, a propylene-alpha-olefin copolymer, and apropylene-ethylene-alpha-olefin copolymer, or mixtures of two or morethereof.
 16. The polypropylene-based composite according to claim 7,wherein the alpha-olefin comonomer is included in an amount of 90 wt %or less, based on the total weight of the copolymer.
 17. Thepolypropylene-based composite according to claim 10, where thetransition metal compound of Formula 1 is Formula 1-1 below:


18. The olefin-based polymer according to claim 10, wherein the hydrogengas is injected in an amount of 0.35 to 3 parts by weight based on 1part by weight of the olefin-based monomer.